Preparation of highly basic,sulfurized alkylphenols

ABSTRACT

A COMBINED PROCESS FOR SULFURIZING AND OVERBASING OF ALKYLPHENOLS IS DISCLOSED. BRIEFLY, THE PROCESS COMPRISES THE STEPS OF: (A) FORMING AN ADMIXING OF ALKYLPHENOL, VOLATILE PROCESS SOLENT, AND WATER, (B) ADDING TO THE ADMIXTURE OF STEP (A) THE AMOUNT OF MAGNESIUM AND/OR CALCIUM ALKOXY ALKOXIDE-CARBONATE COMPLEX REQUIRED FOR OVERBASING, (C) ADDING TO THE ADMIXTURE OF STEP (B) THE AMOUNT OF MAGNESIUM AND/OR CALCIUM ALKOXY ALKOXIDE-CARBONATE COMPLEX REQIURED FOR NEUTRALIZATION, AND (D) REMOVING THE VOLATILE MATERIALS BY HEATING, SAID PROCESS BEING CHARACTERIZED FURTHER IN THAT THE AMOUNT OF SULFUR REQUIRED FOR SULFURIZATION OF THE ALKYLPHENOL IS ADDED AT ANY TIME PRIOR TO STEP (D). THE PRODUCTS ARE PARTICULARLY USEFUL AS ADDITIVE AGENTS FOR LUBRICATING OILS.

United States Patent PREPARATION OF HIGHLY BASIC, SULFURIZED ALKYLPHENOLS Mack W. Hunt and Lynn C. Rogers, Ponca City, Okla., assignors to Continental Oil Company, Ponca City, Okla.

No Drawing. Filed Nov. 10, 1971, Ser. No. 197,519 Int. Cl. C07c 149/38 U.S. Cl. 260-137 26 Claims ABSTRACT OF THE DISCLOSURE A combined process for sulfurizing and overbasing of alkylphenols is disclosed. Briefly, the process comprises the steps of:

(a) forming an admixture of alkylphenol, volatile process solvent, and water,

(b) adding to the admixture of step (a) the amount of magnesium and/ or calcium alkoxy alkoxide-carbonate complex required for overbasing,

(c) adding to the admixture of step (b) the amount of magnesium and/ or calcium alkoxy alkoxide-carbonate complex required for neutralization, and

(d) removing the volatile materials by heating,

said process being characterized further in that the amount of sulfur required for sulfurization of the alkylphenol is added at any time prior to step (d). The products are particularly useful as additive agents for lubricating oils.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is related to the following commonlyassigned applications, which have the same inventors as the present application:

Ser. No. 148,262 filed May 17, 1971 Ser. No. 176,676 filed Aug. 31, 1971 DISCLOSURE Background The use of alkaline earth metal salts of both alkylphenates and sulfurized alkylphenates as additives for lubricating oils has been known for many years. Lubricating oils containing these materials can be used in either internal combustion engines or diesel engines. The presence of these materials in the lubricating oils improves the detergency characteristics, reduces engine wear, minimizes the formation of harmful deposits on engine parts, and improves the resistance of the oil to oxidation.

Still further, the use of highly basic alkaline earth metal salts of alkylphenates or sulfurized alkylphenates as additives in lubricating oils has been known for several years. The term highly basic refers to materials containing an excess of alkaline earth metal basic compounds over the amount of alkaline earth metal required to neutralize the alkylphenol or sulfurized alkylphenol. The presence of these basic alkaline earth metal compounds serves to neutralize acidic materials formed during combustion of the fuel used.

Heretofore, usually, highly basic alkaline earth metal sulfurized alkylphenates have been prepared using one of the following methods. One method uses a commercially available sulfurized alkylphenate. The second method uses a two-step procedure wherein the neutral sulfurized "ice alkylphenate is prepared in the first step and the highly basic sulfurized alkylphenate is prepared in the second step.

The present invention is directed to a combined or onestep process for overbasing and sulfurizing alkylphenols. The process is referred to as one-step in that both overbasing and sulfurizing are effected prior to removing volatile solvents.

The process has the advantage of being more eflicient While also preparing an outstanding product.

It should be noted that the terms highly basic and overbased are used synonymously herein.

Prior art As a result of a prior art search the following references are considered to be the most pertinent.

U.S. Pat. No. 2,788,325 teaches the use of magnesium alkoxy alkoxides to prepare neutral magnesium phenates. The patent teaches the use of temperatures between 100 C. and 250 C. and substantially anhydrous conditions.

U.S. Pat. No. 3,528,917 teaches the preparation of normal (or neutral) calcium sulfurized alkylphenate by the sequential or simultaneous reaction of alkylphenol with a calcium alkoxy alkoxide and sulfur in the presence of a hydrocarbon lubricating oil. The patent teaches that preferably the alkylphenol is sequentially contacted with calcium alkoxy alkoxide to form normal calcium alkylphenate followed by a sulfur contact to form the sulfurized normal calcium alkylphenate.

U.S. Pat. No. 3,474,035 (035) teaches the preparation of an overbased calcium sulfurized alkylphenate from the normal calcium sulfurized alkylphenate of U.S. 3,528,917. According to the process of 035, the normal calcium sulfurized alkylphenate is contacted with a calcium alkoxy alkoxide to form an overbased product having a calcium metal ratio of from 1.1 to about 3.5 and then contacting the product with water in a manner to afiect between about 20 and percent of the overbased product followed by a substantial removal of any unreacted Water.

The process of our invention differs from the processes of the patents described in the foregoing in at least the following ways:

(1) it uses a magnesium or calcium alkoxy alkoxide-carbonate complex (that is, a carbonated magnesium or calcium alkoxy alkoxide),

(2) it uses a one-step procedure as described hereinbefore, and

(3) the dispersed material is predominantly magnesium carbonate, calcium carbonate, or mixtures thereof.

It should be emphasized at this time that substitution of a magnesium alkoxy alkoxide for a magnesium alkoxy alkoxide-carbonate complex in our process does not produce a satisfactory product.

In addition to the aforementioned U.S. patents, the prior art search uncovered the following U.S. patents: 2,703,786; 3,178,368; 3,336,224; 3,388,063; and Re. 26,811. Inasmuch as the latter-mentioned patents are considered to be even less pertinent than the ones discussed, it is not believed necessary to provide any discussion of them herein.

BRIEF SUMMARY OF THE INVENTION Broadly stated, the present invention is a process for preparing highly basic magnesium and calcium salts of sulfurized alkylphenols, wherein the process comprises the steps of:

(a) forming an admixture of alkylphenol, volatile process solvent and water,

(b) adding to the admixture of step (a) the amount required for overbasing of an alkoxy alkanol solution of a calcium or magnesium alkoxy alkoxide-carbonate complex, or mixtures thereof,

() adding to the admixture of step (b) the amount required for neutralization of an alkoxy alkanol solution of a calcium or magnesium alkoxy alkoxide-carbonate complex, or mixtures thereof, preferably while maintaining the temperature higher than that of step (b), and (d) heating to remove the volatile materials,

said process being characterized further in that the amount of sulfur required for sulfurization of the alkylphenol is added prior to removing volatile materials.

In order to prepare a product having a satisfactory viscosity, a nonvolatile diluent oil is usually added. This can be added at any step during the process or to the product. It should be emphasized that the nonvolatile diluent oil is not absolutely essential.

The salient features of the process of our invention are: (1) use of the calcium and/or magnesium alkoxy alkoxide-carbonate complex and (2) adding the sulfur prior to heating to remove volatile materials. Other important features of the process, as well as the amounts of the various materials, will be stated in the detailed description.

DETAILED DESCRIPTION Materials used Suitable alkylphenols for use in our process are represented by the formula wherein R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from 4 to 30 carbon atoms, preferably from 9 to 15 carbon atoms, and n is an integer having a value of l or 2. The total number of carbon atoms for the alkyl groups has a minimum value of 8 and a maximum value of 40. Thus, when n is 1 the minimum number of carbon atoms in R is 8.

Examples of suitable hydrocarbon radicals include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, hexacosyl and triacontyl; radicals derived from petroleum hydrocarbons such as white oil, wax and olefin polymers (e.g. polypropylene and polybutylene).

Products prepared without adding any non-volatile diluent oil are usually solid at ambient temperature since only a smal amount of oil is normally present in the alkylphenol. Accordingly, it is usual practice to add some nonvolatile diluent oil in order to reduce the viscosity of the final product mixture. Since reduction of viscosity is the principal requisite, a wide variety of nonvolatile diluent oils are suitable. The nonvolatile diluent oils have a boiling point in excess of about 200 C.

Examples of suitable nonvolatile diluent oils which can be used include mineral lubricating oils obtained by conventional refining procedures; synthetic lubricating oils such as polymers of propylene, polyoxyalkylenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids or phosphorus; synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C -C alpha-olefins; vegetable oils, such as corn oil, cottonseed oil, and castor oil; animal oils, such as lard oil and sperm oil. Mixtures of these materials can also be employed as the nonvolatile diluent.

Of the preceding examples of nonvolatile diluent oils the mineral lubricating oils and the synthetic lubricating oils are considered more suitable, with the mineral lubricating oils being preferred.

Suitable process solvents for use in our process have a boiling point below about 190 0., preferably below about 150 C. Examples of suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane, heptane, petroleum naphtha, alkoxy alkanols, as defined hereinafter, and primary aliphatic C -C alcohols.

Suitable alkaline earth metals for forming the salts of the sulfurized alkylphenols and for forming the dispersed metal compound are calcium and magnesium. It is to be understod that mixtures of calcium and magnesium are suitable. This includes processes where both are used for forming the phenate and dispersed metal and where one is used for forming the phenate and the other is used for forming the dispersed metal compound.

Our process uses an alkoxy alkanol solution of a calcium or magnesium alkoxy alkoxide-carbonate complex or mixtures thereof. The term alkoxy alkanol as used herein refers to materials represented by the formula ROCH CH O H where R is a C to C alkyl group. Methoxyethanol is the most suitable alkoxy alkanol. The alkoxy alkanols are available commercially under the trademark Cellosolve, methyl Cellosolve, and butyl Cellosolve.

The calcium and magnesium alkoxy alkoxide-complexes are represented by the formula:

M is magnesium or calcium R is a C to C alkyl group, and

X is a number of from 0.5 to 1.5, preferably from 0.85

Weight percent Suitable Preferred Calcium 0.517.0 4.0-10.0 Magnesium"-.- 0.5l1.0 3.0-9.5

The magnesium intermediate is prepared by reacting the magnesium with the alkoxy alkanol followed by carbonation. The calcium intermediate is prepared by reacting an alkoxy alkanol with calcium metal, calcium hydride or calcium carbide, followed by carbonation.

Additional information concerning the preparation and properties of the magnesium and calicum intermediates can be found in US. Pat. No. 3,150,089 and 3,150,088, respectively, which patents are made a part of this disclosure.

Any commercial grade of sulfur can be used in our process provided it is in the form of small particles. Powdered sulfur is particularly suitable.

The water requirements of the process of our invention can 'be met using water -per se, alkoxy alkanol-water mixtures, or aliphatic alcohol-water mixtures.

In some instances it is desirable to use a small amount of an oil-soluble sufonic acid in the process of our invention. We have found that use of such a material results in certain improved properties of the product. For example the BS. & W., which is a measure of the amount of sediment on dilution, is improved. When used preferably the amount of oil-soluble sulfonic acid is from about 0.1 to about 50 parts per parts of alkylphenol or sulfurized alkylphenol.

When using the oil-soluble sulfonic acid preferably a volatile hydrocarbon solvent (e.g. hexane) containing the oil-soluble sulfonic acid is used. The term oil-soluble sulfonic acid is well known in the art. In general, it refers to materials wherein the hydrocarbon portion of the molecule has a molecular weight in the range of about 300 to about 1,000, preferably in the range of about 370 to about 700.

Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually alkylbenzenes being either monoor di-alkyl substituted. The alkyl groups have sufficient carbon atoms to attain the requisite molecular weight range described in the foregoing.

While the term oil-soluble sulfonic acid is believed to be very well understood in the art, in order to make my disclosure even more complete, US. Pat. No. 3,525,599 to Gerald L. Nield, is made a part of this disclosure.

The amounts of the various materials used in our process, both suitable and preferred ranges, are shown below in parts by weight:

1 As indicated hereinbefore, the nonvolatile diluent oil is not essential.

' When used these are the suitable and preferred ranges.

Z The amount of water is also from about 0.75 to about 3.0 moles, preferably from about 1.05 to about 2.0 moles per mole of dispersed magnesium and/or calcium (total amount) present in the final product.

Process conditions In conducting the process of our invention, there is first formed an admixture, in a suitable reaction vessel, of the alkylphenol, volatile process solvent, and water. It is very desirable that the amount of Water used (as defined hereinbefore) be present prior to the addition of the calcium or magnesium intermediate. In those cases where it is desired to use an oil-soluble sulfonic acid, this material is added to this mixture at this point.

To the initial admixture there is then added an overbasing amount (from about 0.10 to about 5 equivalents of metal per equivalent of alkylphenol) of calcium or magnesium intermediate. The overbasing amount of the calcium or magnesium intermediate, or mixtures thereof, is added while maintaining the temperature of the admixture in the range of about 15 to about 100 0., preferably in the range of about 20 to about 75 C., and more preferably in the range of about 25 to about 55 C. While the time of adding the overbasing amount of the calcium of magnesium metal is not particularly critical, it is desirable that this addition occurs in a time period of from about 5 to about 180 minutes, preferably from about 30 to about 120 minutes.

A neutralizing amount (from about 0.95 to about 1.25 equivalent of metal per equivalent of alkylphenol) of calcium or magnesium intermediate, or mixtures thereof, is then added to the admixture. During this step, the admixture is maintained at a temperature of between 50 and about 100 C., preferably from about 55 to 80 C. Most preferably, the temperature in this step is higher than that of the overbasing step. In order to complete the neutralization reaction, it may be desirable to reflux the admixture at this point for a time period of about 5 to about 180 minutes, preferably from about 30 to about 120 minutes.

The required amount of sulfur can be added to the admixture at any time up through this step. In other Words, the sulfur can be added to the initial admixture in any step up through the neutralizing step. Generally, it is desirable to agitate the admixture after adding the sulfur. We have found that adding the sulfur after heating has begun to remove the volatile materials results in a substantial increase of the sediment, as measured by the B.S. & W. test.

The admixture is heated to a suitable temperature to remove the volatile materials present. It is apparent that the temperature required at this point is controlled by the boiling points of the volatile materials present. Temperatures in the range of to 190 C. are employed with the temperature range usually being about 140 to about C. Following removal of the volatile materials the admixture is heated and contacted with carbon dioxide at a temperature in the range of about 140 to about 200 C. Blowing with carbon dioxide at this point serves to substantially complete the carbonation of the magnesium or calcium compound and to remove traces of volatile materials. Knowing that this is the purpose of blowing with CO at this point anyone skilled in the art can readily determine the amount of time required. We have found time periods in the range of 15 minutes to 24 hours to be satisfactory, usually a time period in the range of about 30 minutes to 12 hours is satisfactory.

As stated herein'before in order to prepare a product having a satisfactory viscosity usually a nonvolatile diluent oil is added. The nonvolatile diluent oil can be added at any step during the process or to the product. -It is convenient to add the nonvolatile diluent oil to the initial admixture or to the product after removing volatile materials. Also, it is convenient to add a major portion of the nonvolatile diluent oil to the initial admixture followed by adding an amount to the final product to produce the desired viscosity. In addition to adjusting the product viscosity, the nonvolatile diluent oil can serve to adjust the product activity (i.e., the concentration of alkylphenate and dispersoid materials).

In some instances it may be desired to remove traces of sediment or oil-insoluble residue by filtering the product through a filter aid or by centrifuging.

Manner of defining dispersed metal content of products of our process Two methods of stating the amount of dispersed metal compounds are generally used in this field. One method states the dispersed metal compound as the base number which refers to milligrams of potassium hydroxide per gram of sample. Preferably the base number is an acetic base number referring to an acetic acid titration method which utilizes glacial acetic acid and a solution of perchloric acid in glacial acetic acid as the titrant.

A second method uses the term metal ratio which is defined as the ratio of excess equivalents of metal in the composition to the equivalents of metal theoretically combinable as a normal salt with the alkylphenol or sulfurized alkylphenol.

Inasmuch as the neutral phenate or sulfurized neutral phenate titrates with the perchloric acid, this method has meaning only when the activity (i.e., amount of neutral phenate) is stated. (This statement does not apply to overbased sulfonates.) For the foregoing reason the metal ratio method is preferred.

The products of our invention suitably have a metal ratio in the range of about 0.05 to about 5.0, preferably in the range of about 0.4 to about 2.0.

In order to disclose the nature of the present invention still more clearly, the following examples, both illustrative and comparative, will be given. It is to be understood that the invention is not to be limited to these specific conditions or detail set forth in these examples except insofar as such limitations are specified in the appended claims. Unless stated otherwise, the amounts of materials are stated as parts by weight.

EXAMPLE 1 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium sulfurized alkylphenate.

Materials used: Parts Alkylphenol 2,297 Naphthenic lubricating oil 835 n-Hexane 1,600 Methoxyethanol 400 Water 128.9 Sulfonic acid 222.5 Mg Intermediate 4 2,930 Sulfur (powdered) 200 A predominantly C12 mono-branched alkylphenol, having an average molecular weight of 261 and containing 52.2 weight percent dodecy lphenol, 22.9 weight percent undecyl' phenol, and 7 .5 percent free oil, with the remainder being mixture of predominantly monoalkylphenols.

Having a viscosity of 300 SSU at 100 F.

3 Hexaue solution of sulfonic acid, having a sulfonic acidity 02 452398 rug/gram and a sulfonic acid combining weight A methoxyethanol solution of magnesium methoxyethoxide-carbonate complex containing 7.75 percent (weight) Mg.

Process The following materials were added to a 12 liter, 3- necked, creased flask equipped with a heating mantle and mechanical stirrer: alkylphenol, naphthenic lubricating oil, hexane solution of sulfonic acid, n-hexane and methoxyethanol. After mixing these materials well, the water was added to the admixture. While gradually heating from 26.5 to 51.5 C. over a 60-minute time period, 1,465 grams 0/: of total amount) of the magnesium intermediate was added to the admixture by means of a Tygon tube submerged under the liquid surface. The resulting admixture was then heated to reflux temperature (70- 72 C.). While maintaining the admixture at reflux temperature over a time period of 60 minutes, there was added 1,465 grams of the magnesium intermediate using the submerged Tygon tube as described in the foregoing. At this point, the sulfur was added to the admix ture. The solvents were removed by heating to a liquid temperature of 140 C. The product was then blown with CO gas at 150-195 C. for about two hours. The yield of product was 4,043 grams.

In order to obtain an additional quantity of sample, the preparation was duplicated. The combined products were filtered while hot (about 100 C.) through a diatomaceous earth filter aid to remove traces of sediment.

Product analyses and properties Examples 2-6 illustrate the efiect of adding the sulfur at difierent stages in the process.

EXAMPLE 2 This example illustrates adding the sulfur to the initial admixture.

Materials used: Parts Alkylphenol 172.7 n-Hexane 130 Methoxyethanol 40 Water 2 10.6 Magnesium intermediate 3 217.0 Sulfur (powdered) 15.8 Sulfonic acid 20.5 Naphthenic lubricating oil 5 160 1 Same as footnote in Example 1. 2 About 1.6 moles water/mole MgCOn for overbasing. M Similar to Example 1, but containing 7.86 percent (weight) Hexaue solution of sulfonic acid, containing 28.65 per- 2881?: (weight) sulfonic acid having a combining weight of 5 Same as footnote 2 in Example 1.

Process To a one-liter, 3-necked flask equipped with reflux condenser, heating mantle, thermometer and mechanical stirrer there was added: alkylphenol, hexane, methoxyethanol, hexane solution of sulfonic acid, and sulfur. The materials were mixed well whereupon the water was added. One-half of the magnesium intermediate solution was added gradually over a one-hour time period while slowly heating the admixture from 25 to 55 C. The admixture was then heated to reflux temperature (7074- C.) whereupon the remainder of the magnesium intermediate was added over a one-hour time period while stirring at reflux temperature. The volatile process s01- vents were removed by distillation to a product temperature of 180 C. At this point, the naphthenic lubricating oil was added to adjust the product viscosity. While heating the product at 160-180 C., it was blown with CO gas for one hour in order to remove the last traces of volatile components. The yield of product was 408.4 grams.

The product analyses and properties of this example are shown in Table I.

EXAMPLE 3 This example illustrates adding the sulfur after the overbasing step and prior to distillation to remove volatile materials. Materials used were the same as in Example 2, except that the amount of naphthenic lubricating oil was 150 grams.

Process EXAMPLE 4 This example illustrates adding the sulfur after the addition of the first part of the magnesium intermediate followed by heating to reflux temperature and prior to adding the second part of the magnesium intermediate. Materials used were the same as in Example 3.

Process The process was the same as in Example 3 with the exception described above. The yield of product was 395.6 grams.

The product analyses and properties are shown in Table I.

EXAMPLE 5 This example illustrates adding the sulfur during the distillation step to remove the volatile materials. Materials used were the same as in Example 3.

Process The process was similar to Example 3 with the exception that the sulfur was added in the manner described immediately above. The temperature at the time of sulfur addition was C.

The product analyses and properties are shown in Table I.

EXAMPLE 6 This example also illustrates adding the sulfur during the distillation step to remove the volatile materials. Materials. Materials used were the same as in Example 2.

Process The process of this example was the same as that described in Example with the exception that the temperature at the time of sulfur addition was 100 C.

The product analyses and properties are shown in Table I.

TABLE I Example number Imme- After diately During Initial overprior to removal admixbasing overoivola- Same as When sulfur added. ture step basing tiles Example 5 Sulfur addition I temp, 25 73 71 130 100 Product B.S. & W.,

percent 1 0. 4 0. 5 1. 5 3. 5 4. 0 Viscosity, cs. at 210 F. 45. 1 50. 1 68. 7 69. 9 81.8 Acetic base number... 187 196 190 192 190 Metal ratio 1. 29 1. 29 1. 29 1. 29 l. 29 Magnesium, wt.

percent 4. 38 4. 30 4. 26 4. 22 4. 28 Sulfur, Wt. percent 1. 9 1. 93 1. 85 5. 29 3. 42

! Unfiltered.

EXAMPLE 7 The example illustrates the preparation of a dispersion of calcium carbonate in a calcium sulfun'zed alkylphenol.

carbonate complex containing 7.42 percent (weight) calcium and 8.23 percent (Weight) CO2 Process To a one-liter, 3-necked, creased flask equipped with stirrer, reflux condenser, and thermometer. were added: alkylphenol, n-hexane, methoxyethanol, hexane solution of sulfonic acid, and water. An amount of 137 grams (onehalf of total amount) of the calcium intermediate was added over a period of about one hour with the temperature being at ambient temperature using a Tygon tube as described in Example 1. During the addition of the calcium intermediate, the temperature of the mixture was gradually raised from 25 to 48 C. While stirring the admixture at reflux temperature (73-74 C.) a second 137 gram portion of calcium intermediate was added gradually over a period of one hour. Thereupon the powdered sulfur was added to the admixture. Heating of the admixture to remove solvents was begun. When the temperature was at 120 C., 102 grams of the naphthenic lubricating oil was added. The heating was continued to a temperature of about 150 C. The product was blown with CO gas for one hour while heating at 160180 C. An additional 2 grams of naphthenic dilute oil was added to produce a final product weight of 300 grams.

The analyses and properties of the product were as follows:

10 'EXAMPLE 8 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium sulfurized alkylphenol. The alkylphenol used consisted predominantly of monononylphenol and dinonylphenol.

1 This alkylphenol had an average molecular weight of 262 and the following composition:

Wt. percen Paraffinic hydrocarbons and non-phenols Phenol Octylphenol Nonylphenol Decylphenol Octyl-nonylphenol Dinonylphenol Nonyldecylphenol Miscellaneous Total 99.9

2 A methoxyethanol solution of magnesium methoxyethoxide-carbonate complex containing 7.86 percent (weight) magnesium and 14.2 percent (weight) C02.

3 Same as footnote 1 in Example 1.

4 Same as footnote 4 in Example 2.

N peas-weer (OCDNWCDNEDOQ Process The following materials were added to a one-liter, 3- necked creased flask equipped with heating mantle and mechanical stirrer: alkylphenol, n-hexane, methoxyethanol, sulfonic acid, and water. After mixing these materials well, one-half of the magnesium intermediate was added over a 60-minute time period while gradually heating the admixture from 25 to 55 C. The admixture was then heated to reflux temperature (about 707 3 C.) and the remaining one-half of the magnesium intermediate was added over a 60-minute time period. The sulfur was then added at this point. The solvents were removed by heating to a temperature of C. The product was then blown with CO gas for one hour while remaining at a temperature in the range of -l80 C. During the early part of this CO blowing, when the temperature was about 160 C., the naphthenic lubricating oil was added to the product. Also, a small sample was removed by the B. S. & W. test. While hot the product was filtered through a diatornaceous earth filter aid. The product had the following analyses and properties:

The product yield was 395.6 grams.

EXAMPLE 9 This example also illustrates the preparation of a dispersion of magnesium carbonate in a magnesium sulfurized alkylphenol. The alkylphenol used was a mixture of monononylphenol and dinonylphenol.

Materials used Same as in Example 8 with the exception that a slightly different alkylphenol was used. The amounts of materials were exactly the same. The alkylphenol used had an aver- 1 1 age molecular weight of 246 and the following composi tion:

Process The process was the same as in Example 8. The yield of final product was 395 .6 grams.

The product had the following analyses and properties:

B. S. & W., wt. percent:

Before filtration 4.5

After filtration Trace Acetic base number 191 Metal ratio 1.0

Mg, wt. percent 4.28

Sulfur, wt. percent 3.96

EXAMPLE This example is comparative and shows that the use of a magnesium alkoxy alkoxide instead of a magnesium alkoxy alkoxide-carbonate complex in the process of our 1 Same as footnote 1 in Example 1.

2 :Same as footnote 2 in Example 1.

8 Same as footnote 4 in Example 2.

4 A methoxyethanol solution of magnesium methoxyethoxide containing 9.2 percent magnesium.

Process The following materials were added to a one-liter, 3- necked flask, equipped with heating mantle, thermometer, reflux condenser, and mechanical stirrer: alkylphenol, naphthenic lubricating oil, n-hexane, sulfonic acid, methoxyethanol, sulfur and water. While agitating the mixture vigorously 62.5 grams /2 of total amount) of the uncarbonated magnesium intermediate was added to the mixture gradually over a 60-minute time period while heating from 25 to 55 C. The admixture was heated to reflux and a second 62.5 gram portion of uncarbonated magnesium intermediate was added gradually over a 60- minute period at 79-82 C. However, as the second portion of the magnesium intermediate was being added the admixture became very viscous and gelatinous. About 50 grams of benzene were added in an attempt to fluidize the mixture. Mixing was very poor due to the viscous nature of the product. After addition of the uncarbonated magnesium intermediate was completed, the admixture was heated to 160 C. to remove solvents. It was necessary during this heating to add another 40 grams of naphthenic lubricating oil in order to keep the product of manageable consistency. Finally, the product was blown with nitrogen gas at 160-180 C. for one hour. The product yield was 340.4 grams. The product was an extremely viscous material, which was hard and rubbery at room temperature, and incompatible in SAE 50 lubricating oil.

While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto, since many modifications may be made; and it is, therefore, contemplated to cover by the appended claims any such modifications as fall within the true spirit and scope of the invention.

What is claimed is:

1. A process for preparing highly basic metal salts of sulfurized alkylphenols, wherein the metal is magnesium, calcium or mixtures thereof, wherein the process comprises:

(a) forming an admixture of (i) about 4 to about 80 parts by weight of an alkylphenol represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical, having from 4 to 30 carbon atoms and n is an integer having a value of 1 or 2, said alkylphenol being characterized further in that the total number of carbon atoms is from 8 to 40.

(ii) from about 0.5 to about 200 parts by weight of a volatile process solvent having a boiling point below about 190 C., and

(iii) from about 0.2 to about 14 parts by weight water,

(b) while the temperature is in the range of about 15 to about C., adding to the admixture of step (a) an overbasing amount, in the range of about 0.10 to about 5 equivalent of metal per equivalent of alkylphenol, of a metal intermediate selected from the group consisting essentially of:

(i) a magnesium intermediate containing from about 0.1 to about 11 percent by weight magnesium,

(ii) a calcium intermediate containing from about 0.1 to about 17 percent by weight calcium, and

(iii) mixtures of said magnesium and calcium intermediates,

(c) while maintaining the admixture at a temperature in the range of about 50 to about 100 C., adding thereto a neutralizing amount of from about 0.95 to about 1.25 equivalent of metal per equivalent of alkylphenol of a metal intermediate selected from the group consisting of:

(i) a magnesium intermediate containing from about 0.1 to about 11 percent by weight magnesium,

(ii) a calcium intermediate containing from about 0.1 to about 17 percent by weight calcium, and

(iii) mixtures of said magnesium and calcium in termediates, and

(d) removing the volatile materials by heating, said process being characterized further in that (i) from about 0.5 to about 20 parts by weight of sulfur are added prior to removing the volatile materials by heating in step (d),

(ii) said magnesium intermediate and said calcium intermediate being an alkoxy alkanol solution of a magnesium alkoxy alkoxide-carbonate complex or a calcium alkoxy alkoxide-carbonate complex, wherein the alkoxy alkanol is represented by the formula ROCH3CH2OH with R being a C to C alkyl group and the magnesium and calcium alkoxy alkoxide complexes are'represented by the formula 0 I] M(ooH2oH2oR), x(o-o-0ornomom wherein 13 M is magnesium or calcium R is a C to C alkyl group, and X is a number from 0.5 to 1.5, and (iii) the amount of water in step (a) (iii) is sufficient to provide about 0.75 to about 3.0 moles per mole of dispersed magnesium or calcium.

2. The process of claim 1 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C -C alcohols, and alkoxy alkanols containing from 3 to 8 carbon atoms.

3. The process of claim 2 wherein the temperature of the admixture in step (b) is in the range of about 20 to about 75 C.

4. The process of claim 3 wherein the temperature of the admixture in step (c) is in the range of about 55 to about 80 C.

5. The process of claim 4 wherein (a) the temperature in step (b) is in the range of about 25 to about 55 C., and (b) the temperature in step (c) is higher than that of step (b).

6. The process of claim 5 wherein the amount of water in step (a) (iii) is sufiicient to provide about 1.05 to about 2.0 moles per mole of dispersed magnesium or calcium.

7. The process of claim 6 wherein the process solvent is a mixture of an aliphatic hydrocarbon and a C -C alkoxy alkanol.

8. The process of claim 7 wherein the process solvent is a mixture of hexane and methoxyethanol.

9. The process of claim 7 wherein the final product contains from about 4 to about 95 parts by weight of nonvolatile diluent oil having a boiling point above 200 C.

10. The process of claim 9 wherein the nonvolatile diluent oil is a mineral lubricating oil.

11. The process of claim 10 wherein the product is a magnesium salt of a sulfurized alkylphenol and a magnesium intermediate is employed in steps (b) and (c).

12. The process of claim 10 wherein the product is a calcium salt of a sulfurized alkylphenol and a calcium intermediate is used in steps (b) and (c).

13. A process for preparing highly basic metal salts of sulfurizcd alkylphenols, wherein the metal is magnesium, calcium or mixtures thereof, wherein the process comprises:

(a) forming an admixture of (i) about 9 to about 70 parts by weight of an alkylphenol represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical, having from 4 to 30 carbon atoms and n is an integer having a value of 1 or 2, said alkylphenol being characterized further in that the total number of carbon atoms is from 8 to 40.

(ii) from about 0.2 to about 80 parts by weight of a volatile process solvent having a boiling point below about 190 C., and

(iii) from about 0.3 to about 10 parts by weight water,

(b) while the temperature is in the range of about 20 to about 75 C., adding to the admixture of step (a) an overbasing amount, in the range of about 0.10 to about 5 equivalent of metal per equivalent of alkylphenol, of a metal intermediate selected from the group consisting essentially of:

(ii) a magnesium intermediate containing from about 0.1 to about 11 percent by weight magnesium,

(ii) a calcium intermediate containing from about 0.1 to about 17 percent by weight calcium, and

(iii) mixtures of said magnesium and calcium intermediates,

(c) while maintaining the admixture at a temperature in the range of about 55 to about C., adding thereto a neutralizing amount of from about 0.90 to about 1.25 equivalent of metal per equivalent of alkylphenol, of a metal intermediate selected from the group consisting of:

(i) a magnesium intermediate containing from about 0.1 to about 11 percent by weight magnesium,

(ii) a calcium intermediate containing from about 0.1 to about 7 percent by weight calcium, and

(iii) mixtures of said magnesium and calcium intermediates, and

(d) removing the volatile materials by heating, said process being characterized further in that (i) from about 1.0 to about 15 parts by weight of sulfur are added prior to removing the volatile materials by heating in step (d), and

(ii) said magnesium intermediate and said calcium intermediate being an alkoxy alkanol solution of a magnesium alkoxy alkoxide-carbonate complex or a calcium alkoxy alkoxide-carbonate complex, wherein the alkoxy alkanol is represented by the formula ROCH CHgOH with R being a C to C alkyl group and the magnesium and calcium alkoxy alkoxide complexes are represented by the formula wherein M is magnesium or calcium R is a C to C alkyl group, and X is a number from 0.5 to 1.5, and (iii) the amount of water in step (a) (iii) is sufficient to provide about 0.75 to about 3.0 moles per mole of dispersed magnesium or calcium.

14. The process of claim 13 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C -C alcohols, and alkoxy alkanol containing from 3 to 8 carbon atoms.

15. The process of claim 14 wherein the temperature in step (b) is in the range of about 25 to about 55 C. and the temperature in step (c) is higher than that of step (b).

16. The process of claim 15 wherein the amount of water in step (a) (iii) is sufficient to provide about 1.05 to about 2.0 moles per mole of dispersed magnesium or calcium.-

17. The process of claim 16 wherein the process solvent is a mixture of an aliphatic hydrocarbon and a C -C alkoxy alkanol.

18. The process of claim 17 wherein the process solvent is a mixture of hexane and methoxyethanol.

19. The process of claim 18 wherein the final product contains from about 10 to about parts by weight of nonvolatile diluent oil having a boiling point above 200 C.

20. The process of claim 19 wherein the nonvolatile diluent oil is a mineral lubricating oil.

- 21. The process of claim 20 wherein after step (d) the product is blown with CO at a temperature in the range of about to about 200 C.

22. The process of claim 21 wherein the product is a magnesium salt of a sulfurized alkylphenol and a magnesium intermediate is used in steps (b) and (c).

23. The process of claim 21 wherein the product is a calcium salt of sulfurized alkylphenol and a calcium intermediate is used in steps (b) and (c).

24. The process of claim 9 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol.

25. The process of claim 13 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 'parts of oil-soluble sulfonic acid per 100' parts of alkylphenol.

26. The process of claim 21 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol.

References iited LEWIS GOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner U.S. Cl. X.R.

(3 5? TED STATES Mimi @FFFEQE CER'EWHCATE CF @CRECNCN Patent No. 3 7 16 ,698 D d 7- 7-73 Inventofls) Mack W. Hunt and Lynn C. Rogers It is certified that error appeai'a 1n the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 13, line 73, please change "(ii)" to -(i)- Column 14, line 15, please change "7" to --l7-- Column 1 line 37, please change 1! "M(OCH CH O R) (O e-OCH CH OR) V DO Signed and sealed this 25th day of December 1973.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. v RENE D. TEGTMEYER Acting Commissioner of Patents Attesting Officer 

